CN109599554A - A kind of preparation method of manganese monoxide negative electrode material - Google Patents
A kind of preparation method of manganese monoxide negative electrode material Download PDFInfo
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- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 229910003144 α-MnO2 Inorganic materials 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000004087 circulation Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000238370 Sepia Species 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of preparation method of manganese monoxide negative electrode material is to pass through α-MnO respectively using potassium permanganate, water, hydrochloric acid solution, methylimidazole, polyvinylpyrrolidone, methanol, zinc nitrate as raw material2Preparation, the preparation of solution A, the preparation of solution B, the preparation of solution C, centrifuge separation, vacuum drying, calcining.Manganese monoxide combination electrode material purity is high produced by the present invention, purity may be up to 100%, size is small and of uniform size, particle dispersion is good simultaneously, and agglomeration, stable structure will not occur, without the phenomenon that collapses in preparing calcination process, product yield is high, microcosmic upper with similar nanocube particle specific structure pattern, effectively increases manganese monoxide negative electrode material electrochemical stability and cycle performance；Manganese monoxide combination electrode material produced by the present invention has excellent storage lithium performance, and manganese oxide negative electrode material is under 200mA/g current density, and discharge capacity reaches 897mAh/g for the first time, and after recycling 100 times, capacity grows steadily, or even is increased to 1334 mAh/g.
Description
Technical field
The invention belongs to new material technology fields, and in particular to a kind of preparation method of manganese monoxide negative electrode material.
Background technique
Due to the exploitation of the green energy resources such as solar energy and wind energy and the application of electric car, electrochemical energy storage is just becoming more next
It is more important.Compared to other electrochemical energy storage systems, lithium ion battery energy density is high, and cycle performance is superior, can quick charge and discharge
Electricity, long service life, and it is environmentally protective, it is considered as most promising energy storage device.For applied to hybrid-electric car and electricity
Electrical automobile, it is desirable that lithium battery has higher energy density, higher service life, and broader operating temperature uses window.Lithium from
Sub- battery is mainly made of anode, cathode and electrolyte, and battery performance depends primarily on electrode material and electrolyte, wherein cathode
The performance raising of material is critical issue.Graphite is the carbon negative pole material for being applied to lithium ion battery earliest.The theoretical of graphite holds
It is low to measure (372mAh/g), it is difficult to meet the needs of people are to higher capacity, therefore it is very urgent to study novel anode material.
Manganese monoxide is and environmental-friendly, cheap due to having many advantages, such as relatively wide voltage window (1.032V),
Therefore become a kind of more promising lithium ion battery negative material.But there are electric conductivity is poor and charge and discharge for manganese monoxide simultaneously
The violent disadvantage of volume expansion in electric process, leading to it, irreversible capacity is high for the first time, cyclical stability is poor, limits its conduct
The application of lithium ion battery negative material.
The preparation of manganese monoxide at present still has that preparation process skeleton is big, and whole uniformity is poor, and it is pure that electrode material is made
Spend low, size is big, and size is uneven, and particle dispersion is poor, and structural stability is poor, be easy to appear in calcination process collapse it is existing
As yield is low, and electrochemical stability and cyclicity etc. are not ideal enough.
Summary of the invention
It is an object of that present invention to provide a kind of preparation methods of manganese monoxide negative electrode material haveing excellent performance.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of manganese monoxide negative electrode material, which is characterized in that it is with potassium permanganate, water, hydrochloric acid solution, diformazan
Base imidazoles, polyvinylpyrrolidone, methanol, zinc nitrate are raw material, pass through α-MnO respectively2Preparation, the preparation of solution A, solution
The preparation of B, the preparation of solution C, centrifuge separation, vacuum drying, calcining.
Further specifically, above-mentioned α-MnO2Preparation be to take potassium permanganate and deionized water is placed in appropriate vessel,
Speed of agitator be 120 ~ 300r/min, mixing time 10 ~ 15 minutes, make it dissolve, hydrochloric acid solution be then added, continue stirring 5 ~
It 8 minutes, being then transferred in autoclave, setting temperature is 155 ~ 165 DEG C, it reacts 5 ~ 7 hours, after reaction, is centrifugated,
The centrifugal rotational speed is 9000 ~ 11000r/min, and centrifugation time is 3 ~ 5 minutes；Centrifugation terminates, collect precipitating, successively spend from
Sub- water and dehydrated alcohol respectively wash three times, and the quality (g) of the precipitating and the volume (ml) of deionized water are than being 1:60 ~ 100, institute
The quality (g) of precipitating and the volume (ml) of dehydrated alcohol are stated than being 1:60 ~ 100；Sediment after washing is placed at 55 ~ 65 DEG C and does
Dry 5 ~ 7 hours to get α-MnO2；Wherein the concentration of hydrochloric acid is 3mol/L, the quality (g) and deionized water of the potassium permanganate
Volume (ml) than being 1:100 ~ 160, the volume (ml) of the quality (g) of the potassium permanganate and hydrochloric acid solution is than being 1:12 ~ 15.
Further, the preparation of above-mentioned solution A is that methylimidazole and polyvinylpyrrolidone is taken to dissolve under magnetic stirring
In methanol；The preparation of above-mentioned solution B is to take zinc nitrate and α-MnO2It is dissolved in methanol under magnetic stirring, speed of agitator is
120 ~ 300r/min, mixing time are 3 ~ 5 minutes；Wherein, the quality (g) of the methylimidazole, polyvinylpyrrolidone
Quality (g) and the volume (ml) of methanol are than being 0.6 ~ 1.8:0.3 ~ 0.9:10 ~ 30；The quality (g) of the zinc nitrate, α-MnO2's
Quality (g) and the volume (ml) of methanol are than being 0.2 ~ 0.6:0.04 ~ 0.12:20 ~ 60.
Further, the preparation of above-mentioned solution C is to mix solution A obtained above and solution B, speed of agitator is 200 ~
300r/min, mixing time is 20 ~ 24 hours to get solution C, wherein the volume ratio of the solution A and solution B is 1:2.
Preferably, above-mentioned centrifuge separation is to be placed in a centrifuge solution C, and 9000 ~ 11000r/min of revolving speed, centrifugation is arranged
Time is 3 ~ 5 minutes, and centrifugation terminates, and collects precipitating, washs precipitating three times with methanol, quality (g) and the methanol of the precipitating
Volume (ml) ratio is 1:120 ~ 200, and washing terminates, and collects precipitating.
Further, above-mentioned vacuum drying is to take above-mentioned precipitating, is placed in a vacuum drying oven, setting vacuum degree be -2.5 ~ -
3MPa, drying temperature are 60 ~ 80 DEG C, and dry 12 ~ 24 hours to get α-MnO2- ZIF-8 powder, it is spare.
It is highly preferred that above-mentioned calcining is to take α-MnO obtained above2- ZIF-8 powder, under an argon atmosphere, with 2 DEG C/
The heating rate of min is warming up to 200 ~ 300 DEG C and calcines 1 ~ 2 hour, then calcines 3 ~ 5 hours at 900 ~ 1000 DEG C, calcining knot
Beam takes out after being cooled to room temperature to get manganese monoxide composite material.
The present invention have it is following the utility model has the advantages that
Manganese monoxide electrode material purity is high produced by the present invention, purity may be up to 100%, and size is small and of uniform size, while
Grain good dispersion, stable structure, without the phenomenon that collapses in preparing calcination process, product yield is high, microcosmic upper with similar nanometer
Cubic granules specific structure pattern, effectively increases manganese monoxide negative electrode material electrochemical stability and cycle performance；This hair
Bright manganese monoxide negative electrode material obtained has excellent storage lithium performance, manganese oxide negative electrode material under 200mA/g current density,
Discharge capacity reaches 897mAh/g for the first time, and after recycling 100 times, capacity grows steadily, or even is increased to 1334 mAh/g, this
Preparation method economy is simple, easy to operate, is worth marketing.
Detailed description of the invention
Fig. 1 is the XRD diagram of the manganese oxide negative electrode material of Example 1 and Example 2 of the present invention preparation.
Fig. 2 is the SEM figure of manganese oxide negative electrode material prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM figure of manganese oxide negative electrode material prepared by the embodiment of the present invention 2.
Fig. 4 is the FESEM figure of manganese oxide negative electrode material prepared by the embodiment of the present invention 1.
Fig. 5 is the TEM figure of manganese oxide negative electrode material prepared by the embodiment of the present invention 1.
Fig. 6 is the cyclic curve figure of manganese oxide negative electrode material prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
Embodiment 1:
A kind of preparation method of manganese monoxide negative electrode material of the present embodiment, the specific steps of which are as follows:
1. hydrothermal synthesis α-MnO2
It weighs 0.316g potassium permanganate to be dissolved in 30mL deionized water, be mixed 10 minutes in a reservoir, speed of agitator is
200r/min；The hydrochloric acid 3.6mL of 3mol/L is added, continues stirring 5 minutes；It is transferred in autoclave, 160 DEG C of progress hydro-thermal reactions
6 hours, suspended reaction solution is centrifuged, centrifugal rotational speed 10000r/min, centrifugation time 5 minutes, then spend from
Three times, deionized water and dehydrated alcohol dosage are 80ml, and then drying 6 is small at 60 DEG C for sub- water and dehydrated alcohol washing precipitate
When to get sepia α-MnO2Powder.
2. weighing 0.6g methylimidazole and 0.3g polyvinylpyrrolidone being dissolved in wiring solution-forming A in 10mL methanol, stir
Revolving speed is 180r/min, and mixing time is 4 minutes；Weigh 0.3g zinc nitrate and 0.04g α-MnO2It is dissolved in 20mL methanol and being made into
Solution B, speed of agitator 180r/min, mixing time are 4 minutes；
3. 10mL solution A and 20mL solution B are mixed into solution C, stir 24 hours at room temperature, speed of agitator 250r/min；
4. solution C is centrifuged, centrifugal rotational speed 10000r/min, centrifugation time is 3 minutes, is then washed with methanol solution
Wash sediment three times, methanol usage 150ml；
5. sediment is placed in vacuum oven drying at 60 DEG C, vacuum degree is -2.8MPa, and drying time is 24 hours, i.e.,
Obtain shallow sepia α-MnO2- ZIF-8 powder；
6. by α-MnO2With the heating rate of 2 DEG C/min, it is small to be warming up to 280 DEG C of calcinings 2 under an argon atmosphere for-ZIF-8 powder
When, it is then calcined 4 hours at 900 DEG C, calcining terminates, and takes out after being cooled to room temperature to get manganese monoxide composite material.
Fig. 1 is that the manganese monoxide negative electrode material of this example preparation tests resulting XRD diagram through XRD diffractometer.It can from figure
Know, it is a pair of with the diffraction maximum one of standard manganese monoxide and zinc oxide card in the prepared manganese monoxide/composite material of calcining
It answers, and miscellaneous peak is not present, illustrate that purity is high, purity may be up to 100%.Fig. 2 is the manganese monoxide negative electrode material of this example preparation
SEM figure.It can be seen from the figure that 900oThe manganese oxide nano granule good dispersion of C calcining preparation, size is more uniform, structure
Stablize without the phenomenon that collapses, while solving the problems, such as agglomeration techniques.Fig. 4 is the manganese monoxide negative electrode material of this example preparation
FESEM figure.Clearer it can find out from figure, special polyhedron pattern is presented in manganese oxide nano granule, and size is more equal
Even, diameter is in 250 ~ 450nm.Fig. 5 is the TEM figure of the manganese monoxide negative electrode material of this example preparation.It can be seen from the figure that oxygen
Change manganese nano particle and special polyhedron pattern be presented, size is more uniform, stable structure without the phenomenon that collapses, diameter 250 ~
450nm.Fig. 6 is the manganese oxide negative electrode material of the preparation of embodiment 1 under 200mA/g current density, the cycle performance that circulation is 500 times
Curve.Its first discharge specific capacity is 897mAh/g, and with the increase of cycle-index, charging and discharging capacity is all declining, but library
Human relations efficiency is increased to 99% or so, illustrates that battery reversibility improves.Until circulation 100 times, specific discharge capacity 502mAh/g,
Charge specific capacity is 496mAh/g, and coulombic efficiency 98.87%, the circulation after, charging and discharging capacity, which is presented, to grow steadily
Trend.Circulation 200 times, specific discharge capacity 662mAh/g, charge specific capacity 648mAh/g, coulombic efficiency 97.91%；
Circulation 300 times, specific discharge capacity 889mAh/g, charge specific capacity 865mAh/g, coulombic efficiency 97.22%；Circulation 400
It is secondary, specific discharge capacity 1189mAh/g, charge specific capacity 1172mAh/g, coulombic efficiency 98.61%；Circulation 500 times, puts
Electric specific capacity is 1334mAh/g, charge specific capacity 1307mAh/g, coulombic efficiency 97.97%.From integral battery cycle performance
From the point of view of, after 100 circulations, capacity grows steadily, or even is increased to 1334 mAh/g, hence it is evident that is higher than its appearance of discharging for the first time
Amount.
Embodiment 2:
A kind of preparation method of manganese monoxide negative electrode material of the present embodiment, the specific steps of which are as follows:
1. hydrothermal synthesis α-MnO2It is identical as in embodiment 1；
2. weighing 0.6g methylimidazole and 0.6g polyvinylpyrrolidone being dissolved in wiring solution-forming A, speed of agitator in 10mL methanol
For 300r/min, mixing time is 3 minutes；Weigh 0.3g zinc nitrate and 0.04g α-MnO2It is dissolved in wiring solution-forming in 20mL methanol
B, speed of agitator 300r/min, mixing time are 3 minutes；
3. 10mL solution A and 20mL solution B are mixed into solution C, stir 24 hours at room temperature, speed of agitator 280r/min；
4. solution C is centrifuged, centrifugal rotational speed 11000r/min, centrifugation time is 5 minutes, is then washed with methanol solution
Wash sediment three times, methanol usage 200ml；
5. sediment is placed in vacuum oven at 60 DEG C dry, vacuum degree is -3MPa, drying time be 24 hours to get
Shallow sepia α-MnO2-ZIF-8 powder；
6. by α-MnO2With the heating rate of 2 DEG C/min, it is small to be warming up to 300 DEG C of calcinings 1 under an argon atmosphere for-ZIF-8 powder
When, it is then calcined 4 hours at 1000 DEG C, calcining terminates, and takes out after being cooled to room temperature to get a kind of manganese monoxide composite material.
Fig. 1 is that the manganese monoxide negative electrode material of this example preparation tests resulting XRD diagram through XRD diffractometer.It can from figure
Know, the diffraction maximum one in the prepared manganese monoxide composite material of 1000 DEG C of calcinings, with standard manganese monoxide and zinc oxide card
One is corresponding, and miscellaneous peak is not present, and product purity may be up to 100%.Fig. 3 is the SEM of the manganese monoxide negative electrode material of this example preparation
Figure.It can be seen from the figure that 1000oThe manganese oxide nano granule of C calcining preparation is compared in Fig. 2 900oThe manganese oxide ruler of C calcining preparation
Very little smaller, particle is thinner, but Structure Comparison is in 900oThe integrity degree of C is slightly more inferior, while solving the problems, such as agglomeration techniques,
Another experiment shows that manganese monoxide negative electrode material made from embodiment 2 has excellent storage lithium performance.
Claims (7)
1. a kind of preparation method of manganese monoxide negative electrode material, which is characterized in that it is with potassium permanganate, water, hydrochloric acid solution, two
Methylimidazole, polyvinylpyrrolidone, methanol, zinc nitrate are raw material, pass through α-MnO respectively2Preparation, solution A preparation, molten
The preparation of liquid B, the preparation of solution C, centrifuge separation, vacuum drying, calcining.
2. a kind of preparation method of manganese monoxide negative electrode material as described in claim 1, which is characterized in that above-mentioned α-MnO2's
Preparation is that potassium permanganate and deionized water is taken to be placed in appropriate vessel, and speed of agitator is 120 ~ 300r/min, mixing time 10 ~ 15
Minute, it makes it dissolve, hydrochloric acid solution is then added, continue stirring 5 ~ 8 minutes, be then transferred in autoclave, setting temperature is
It 155 ~ 165 DEG C, reacts 5 ~ 7 hours, after reaction, centrifuge separation, the centrifugal rotational speed is 9000 ~ 11000r/min, centrifugation
Time is 3 ~ 5 minutes；Centrifugation terminates, and collects precipitating, is successively respectively washed three times with deionized water and dehydrated alcohol, the precipitating
The volume (ml) of quality (g) and deionized water is than being 1:60 ~ 100, the quality (g) of the precipitating and the volume (ml) of dehydrated alcohol
Than for 1:60 ~ 100；Sediment after washing is placed at 55 ~ 65 DEG C dry 5 ~ 7 hours to get α-MnO2；Wherein the hydrochloric acid is dense
Degree is 3mol/L, and the quality (g) of the potassium permanganate and the volume (ml) of deionized water are than being 1:100 ~ 160, the permanganic acid
The quality (g) of potassium and the volume (ml) of hydrochloric acid solution are than being 1:12 ~ 15.
3. a kind of preparation method of manganese monoxide negative electrode material as claimed in claim 2, which is characterized in that above-mentioned solution A
Preparation is that methylimidazole and polyvinylpyrrolidone is taken to be dissolved in methanol under magnetic stirring；The preparation of above-mentioned solution B is
Take zinc nitrate and α-MnO2It is dissolved in methanol under magnetic stirring, speed of agitator is 120 ~ 300r/min, and mixing time is 3 ~ 5
Minute；Wherein, volume (ml) ratio of the quality (g) of the methylimidazole, the quality (g) of polyvinylpyrrolidone and methanol is
0.6 ~ 1.8:0.3 ~ 0.9:10 ~ 30；The quality (g) of the zinc nitrate, α-MnO2Quality (g) and volume (ml) ratio of methanol be
0.2 ~ 0.6:0.04 ~ 0.12:20 ~ 60.
4. a kind of preparation method of manganese monoxide negative electrode material as claimed in claim 3, which is characterized in that above-mentioned solution C
Preparation is to mix solution A obtained above and solution B, and speed of agitator is 200 ~ 300r/min, and mixing time is 20 ~ 24 small
When to get solution C, wherein the volume ratio of the solution A and solution B is 1:2.
5. a kind of preparation method of manganese monoxide negative electrode material as claimed in claim 4, which is characterized in that above-mentioned centrifuge separation
It is to be placed in a centrifuge solution C, 9000 ~ 11000r/min of revolving speed is set, centrifugation time is 3 ~ 5 minutes, and centrifugation terminates, and collects
Precipitating washs precipitating three times with methanol, and the quality (g) of the precipitating and the volume (ml) of methanol are than being 1:120 ~ 200, washing knot
Beam collects precipitating.
6. a kind of preparation method of manganese monoxide negative electrode material as claimed in claim 5, which is characterized in that above-mentioned vacuum drying
It is to take above-mentioned precipitating, is placed in a vacuum drying oven, setting vacuum degree is -2.5 ~ -3MPa, and drying temperature is 60 ~ 80 DEG C, drying 12
~ 24 hours to get α-MnO2- ZIF-8 powder, it is spare.
7. a kind of preparation method of manganese monoxide negative electrode material as claimed in claim 6, which is characterized in that above-mentioned calcining is to take
α-MnO obtained above2- ZIF-8 powder with the heating rate of 2 DEG C/min, is warming up to 200 ~ 300 DEG C and forges under an argon atmosphere
It burns 1 ~ 2 hour, is then calcined 3 ~ 5 hours at 900 ~ 1000 DEG C, calcining terminates, and takes out after being cooled to room temperature to get manganese monoxide
Composite material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140506A (en) * | 2015-09-30 | 2015-12-09 | 中国科学技术大学 | Three-dimensional porous MnO/C-N nano-composite material based on rape pollen, preparing method thereof and application thereof |
| CN109585822A (en) * | 2018-11-23 | 2019-04-05 | 重庆文理学院 | A kind of preparation method of manganese monoxide/zinc oxide negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140506A (en) * | 2015-09-30 | 2015-12-09 | 中国科学技术大学 | Three-dimensional porous MnO/C-N nano-composite material based on rape pollen, preparing method thereof and application thereof |
| CN109585822A (en) * | 2018-11-23 | 2019-04-05 | 重庆文理学院 | A kind of preparation method of manganese monoxide/zinc oxide negative electrode material |
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| MING ZHONG ET AL.: "Yolk–Shell MnO@ZnMn2O4/N-C Nanorods Derived from α -MnO2/ZIF-8 as Anode Materials for Lithium Ion Batteries", 《SMALL》 * |
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